O-alkyl-o-(1,3-disubstituted-pyrazol(5)yl)-(thiono)-phosphoric(phosphonic)acid esters

ABSTRACT

IN WHICH R is alkyl of one to six carbon atoms, R&#39;&#39; is alkyl or alkoxy of one to six carbon atoms or phenyl, R&#39;&#39;&#39;&#39; is lower alkyl, cyano-lower alkyl or 1,1-dioxythiolane, R&#39;&#39;&#39;&#39;&#39;&#39; is carbalkoxy, carbamoyl, monoalkylcarbomoyl or dialkylcarbamoyl, R&#39;&#39;&#39;&#39;&#39;&#39;&#39;&#39; is hydrogen, chlorine or alkyl or one to six carbon atoms, and X is oxygen or sulfur, WHICH POSSESS INSECTICIDAL, ACARICIDAL AND FUNGICIDAL PROPERTIES.   0-ALKYL-0-(1,3-DISUBSTITUTED-PYRAZOL(5)YL)-(THIONO)-PHOSPHORIC (PHOSPHONIC) ACID ESTERS OF THE GENERAL FORMULA

United States Patent 1191 Hoffman et al.

I l O-ALKYL-O-l IQDISUBSTITUTED- PYRAZOU5)YLl-(TiilONO)-PHOSPHORIC (PHOSPHONIC) AClD ESTERS [7S] inventors: Hellmut Hoflmann. Wuppertal; Ingeborg Hammlnn; Wolfgang Behrenz. both of Kocln. all of Germany [73) Asslgnee: Bayer Alttlengesellachah.

Leverkusen. Germany [22] Filed: Apr. 17, 1973 [21] Appl. No.: 351,891

[30] Foreign Application Priority Data OTHER PUBLICATIONS Ferbenfabriken Bayer A.-G. Chem. Abst. Vol. 74. No. 42383 (197]). QDLASl.

Pudovik et al. Chem. Abst. Vol. 77, No. 485891 (1972). QDLAS].

[ Oct. 22, 1974 rimary Examiner-Natalie Trousoi Attorney, Agent. or Firm-Burgess. Dinklage 8t Sprung [57] ABSTRACT 0-alkyl-O'1 l.3-disubstituted-pyrazol( 5 )yl l-( thiono phosphoric (phosphonic) acid esters of the general formula RI!" no x in which R is alkyl of one to six carbon atoms, R is alkyl or alkoxy of one to six carbon atoms or phenyl, R" is lower alkyl, cyano-lower l,l-dioxythiolane. R is carbalkoxy. carbamoyl. monoalkylcarbomoyl or dialkylcarbamoyl. R"" is hydrogen, chlorine or alkyl or one to six carbon atoms. and X is oxygen or sulfur. which possess insecticidal. acaricidal and fungicidal properties.

alkyl or 7 Claims, No Drawings The present invention relates to and has for its objccts the provision of particular new -alkyl-0-[l,3-disubstituted-pyrazoK )yl]-(thiono)-phosphoric (phosphonic) acid esters which possess insecticidal, acaricidal and fungicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids and fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

it is known from German Published Specification DOS 2,037,853 and USA Patent specification No. 2,754,244 that pyrazolothionophosphoric acid esters, f or example 0,0-dimethyl- (Compound A) or 0,0- diethyl-0-[ l-methyl-4-cyano 5-methylmercaptopyrazolyl(3)]-(Compound B) or 0,0-diethyl-0-[3- methyl-pyrazolyKS)]-thionophosphoric acid esters (Compound C), possess insecticidal and acaricidal properties.

The present invention provides 0pyrazolo(thiono)- phosphoric( phosphonic) acid esters of the general formula in which R is alkyl of one to six carbon atoms,

R is alkyl or alkoxy of one to six carbon atoms or phenyl,

R" is lower alkyl, cyano-lower alkyl or i, l -dioxythiolane,

R' is carbalkoxy, carbamoyl, monoalkylcarbamoyl or dialkylcarbamoyl,

R"" is hydrogen, chlorine or alkyl of one to six carbon atoms, and

X is oxygen or sulfur.

Preferably, R is lower alkyl of one to four carbon :tlOmS, R is lower alkyl or alkoxy or phenyl, R" is lower alkyl of one to four carbon atoms, cyanoethyl, Z-cyanopropyl or 1,l-dioxythioiane, R'" is carbo-lower nlkoxy such as carbomethoxy, carboethoxy or carboisopropoxy, carbamoyl or monoor di-lower alltylcarbamoyl with up to three carbon atoms in each alltyl radical, and R"" is hydrogen, chlorine or lower alkyl such as methyl or ethyl.

Surprisingly, the 0-pyrazolo-(thiono)-phosphoric(- hosphonic) acid esters according to the invention pos- $085 a substantially higher insecticidal and acaricidal action than previously known compounds of analogous structure and similar type of action. They have in par,-

(lltl) ticular proved of value in combating hygiene pests and pests of stored products. The products according to the invention thus represent a genuine enrichment of the art. Furthermore they contribute to satisfying the great demand for constantly new active compounds in the field of pesticides. The latter results from the fact that the commercially available agents have to meet constantly higher standards, especially in respect of the protection of the environment, such as low toxicity to warm-blooded animals and low phytotoxicity. rnpid degradation in and on the plant with short minimum intervals to'be observed between spraying with pesticide and harvesting, and activity. against resistant posts.

The present invention also provides a process for the production of an 0-pyrazolo(thiono)-phosphoric(phosphonic) acid ester of the formula (i) in which a. a (thiono)phosphoric( phosphonic) acid ester halide of the general formula P-Hal (Ill is reacted with a pyrazole derivative of the general formula in the presence of an acid-binding agent or in the form of an alkali metal, alkaline earth metal or ammonium salt, or

b. a trialltylphosphite of the general formula is reacted with a pyrazole derivative of the general formula acid-bind ing agent l CH (Ill!) 0 11 (VII) (c n o) -o- The pyrazole derivatives of the formula (ill) or (V) required as starting substances can, for example, be prepared as follows: starting from the corresponding oxalcarboxylic acid esters and substituted hydrazines, pyrazoles of the structure (Vlll) are obtained, which can be converted, for example with sulfuryl chloride, into the dichlorinated compounds which can then in turn optionally be reduced with reducing agents, for example bisulfite, to the 4-chloro-5-hydroxypyrazole derivatives of the structure (ix):

R" has the above mentioned meaning and R- denotes hydrogen or alkyl with one to six carbon atoms.

in the pyrazoles (IX) thus obtained it is possible, for example, to trans-esterify the carbalkoxy group or to convert it by means of ammonia or primary or secondary amines into an optionally monosubstituted or disubstituted carbamoyl group.

The following may be mentioned individually as examples of pyrazole derivatives to be employed: 1- methyl-, l-ethyl-. l-n-propyl-, l-iso-propyl-. lcyanoethyl-, l-(2'-cyanopropyl)- or l-( l ldioxythiolane)-3-carbomethoxyor -3-carboethoxy-. -3-carbo-n-propoxy-, -3-carbo-isopropoxy-, -3- carbamoyi-, -3-N-methyl-, -3-N-ethyl, -3-N-n-propyl-. -3-N-iso-propyl-, -3-N,N-dimethyl-, -3-N,N-diethylor -3-N,N-dipropyl-carbamoyl- S-hydroxypyrazole, and also the corresponding derivatives substituted in the 4- position by chlorine, methyl or ethyl, as well as the corresponding 4,4-dichloropyrazolinone(5) derivatives.

As examples of (thiono)-phosphoric(phosphonic) acid ester halides to be reacted in the process there may be mentioned: 0,0-dimethyl-, 0,0-diethyi-, 0,0-din-propyl-, 0,0-di-isopropyl, 0,0-di-n-butyl-, 0,0 li-secbutyl-, 0,0-di-isobutyland 0,0-di-tert.-butylphosphoric acid ester chloride and the corresponding thiono analogues, and also O-methyl-, 0-ethyl-, O-npropyl-, 0-isc-propyl-, 0-n-butyl-, 0-sec.-butyl-. O-isobutyl-, 0-tert.-butyl-methane-, -ethane-, -propanc-, -butaneor -phenyl-phosphoric acid ester chloride as well as the corresponding thiono analogues.

The process of the invention is preferably carried out in the presence of a solvent or diluent. As such, practically all inert solvents can be used. These include, in particular, aliphatic and aromatic optionally chlorinated hydrocarbons. The process variant (a) is preferably carried out in benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, an ether, such as diethyl ether or dibutyl ether or dioxane, or a ketone, for example acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, or a nitrile, such as acetonitrile or propionitrile, while the process variant (b) is preferably al lowed to take place in benzene, toluene, xylene, benzine, an ether, for example diethyl ether or dibutyi ether or dioxane, or a ketone, such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, or a nitrile, such as acetonitrile or propionitrile.

All customary acid-binding agents can be used as acid acceptors in process variant (a). Alkali metal carbonates and alkali metal alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate and sodium and potassium ethylate have proved particularly suitable, as have aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperatures can be varied over a wide range. In general the reaction is carried out at about 0 to 120, preferably about 25 to C.

The reaction is generally carried out under normal pressure.

To carry out the process, the starting substances are generally employed in equimolar ratios. The reactions are preferably carried out in the presence of one of the abovementioned solvents at the indicated temperatures, and in the case of process variant (0) additionally, if appropriate, in the presence of an acid acceptor. After several hours reaction, in most cases at elevated temperatures while stirring, the reaction mixture may be worked up in the usual manner.

The compounds according to the invention are in most cases obtained in the form of oils, some of which can not be distilled without decomposition but can be freed of the last volatile constituents by so-callcil slight distillation," that is to say prolonged heating under reduced pressure to moderately elevated temperatures, and can be purified in this manner. They are characterized by their refractive indexes Some of the products are obtained in the form of crystalline compounds of sharp melting point.

As has already been mentioned, the new 0- pyrazolo(thiono)-phosphoric(phosphonic) acid esters are distinguished by an excellent insecticidal and acaracidal activity against plant pests, hygiene pests and pests of stored products. They possess a good action both against sucking and against biting insects and mites (Acarina). At the same time they display a low phytotoxicity accompanied, in some cases, by a fungicidal action.

For these reasons, the compounds according to the invention can be employed successfully as pesticides in plant protection and the protection of stored products, and in the hygiene field.

To the sucking insects there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosip/tum solanifolii), the currant gall aphid (Cryptomyzus korzcheltt'), the res, apple aphid (Sappaphis melt), the mealy plum aphid (Hyaloplerus arundinr's) and the :herry blackfly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Arpidr'otus hederae) and the soft scale (Lzcant'um hespen'dum) as well as the grape mealybug (Pseudoccus maritimus); thn'ps (Thysanoptera), such as Hereinarhrr'ps femoralis, and bugs, for example the beet bug (Piesma quadrara), the red cotton bug (Dysdercus intermedius), the bed bug (Ct'mex lectularius), the assassin bug (Rhodnt'us prolixus) and Chagas' bug (Triatoma infestans) and, further, cicadas, such as Euscelis bt'lobatus and Nephotettix bipunctatus.

in the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoplera) such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the browntail moth (Eupmctis chrysorrhoea) and tent caterpillar (Malacosoma neustria), further, the cabbage moth (Mamestra brarslcae) and the cutworrn (Agmtls regetum), the large white butterfly (Pierts brasslcae), the small winter moth (Chelmatobr'a brumata), the green oak tortrix moth (Torm'x viridana), the fall armyworm (Laphygma frugt'perda) and cotton worm (Prodenla lilura), the ermine moth (Hyponomeum padella), the Mediterranean flour moth (Ephesria kuhmella) and greater wax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Coleoplera), for example the granary weevil (Sirophilus granarr'us Calandra granaria), the Colorado beetle (Leprinolarsa decemlineata), the dock beetle (Gastrophysa virr'dula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byrurus lomentosus), the bean weevil (Bruchidt'us Acanthoscelides obtectus), the leather beetle (Dennestes frischr'), the Khapra beetle (Trogoderma granarr'um), the flour beetle (Trr'bolium castaneum), the northern corn billbug (Calandra or Sitophilus zeamat's), the drugstore beetle (Sregobium paniceum), the yellow mealworm (Tenebrt'o molt'lor) and the saw-toothed grain beetle (Oryzaephilus surinamcnst's), and also species living the the soil, for example wircworms (Agrimer spec.) and larvae of the cockchafer (Melolontha melolonlha); cockroaches, such as the German cockroach (Blarrella germanim), American cockroach (Pert'planera amert'cana), Madeira cockroach (Leueophaea or Rhypamhia maderar'), oriental cockroach (Blarra orienlalis), the giant cockroach (Blaberus gigameus) and the black giant cockroach (Blaberus fuscus) as well as Henschouledenia flexiviuu; further, Orthoprera, for example the house crickci (Acheta domesrr'cus); termites such as the eastern subterranean tennite (Reliculilermes flavipcs) and Hymt'noptera such as anls, for example the garden an! (LdAiuA' niger).

The Diptera comprise essentially the flies, such as thc vinegar fly (Drosophila melanogasrer), the Mediterranean fruit fly (Cerau'tis capilata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Cal- Iiphora erythrocephala) as well as the stable fly (Smmoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi With the mites (Acari) there are classed, in particular, the spider mites (Tetranychidae) such as the twospotted spider mite (Telranychus urticae) and the European red mite (Paratetranychus pilosus Panonychus ulmi), gall mites, for example the black-currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus larus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata).

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the process products are also distinguished by an outstantl ing residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or ex tender: of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dllpenible carrier vehicles such as gases, solutions. emulsions, lulpensions, cmulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents. granules, etc. These are prepared in known manner, for instance by extending the active compounds with con ventional pesticide dispersible liquid diluent carriers and/or dispenible solid carries optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents, The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes. etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc. alcohols (e.g. methanol, ehthanol, propanol, butanol. glycol, etc.) as well as ethers and esters thereof (L' c glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formarrtide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.)', whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc); and/or dispersing agents, such as ligrtin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, and fungicides, or rodenticides, bactericides, nematocides, herbicides, fertilizers, growthregulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95 percent by weight, and preferably 0.5-90 percent by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10 percent, preferably 001-! percent, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and- /or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95 percent, and preferably 0.01-95 percent, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufi'icient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about percent by weight of the active compound or even the per cent active substance alone, e.g. about 20l0() percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids and fungi, and more particularly methods of combating at least one of insects and acan'ds, which comprises applying to at least one of correspondingly (a) such insects, ('2) such acarids, (0) such fungi, and (d) the corresponding habitat thereof. i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricitlally or fungicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing scattering, dusting, watering, squirting, sprinkling. pouring, fumigating, and the like.

it will be realized, of courre, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstand ing activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 The pyrazole derivatives of the formula (ill) or (V) required as starting materials can be prepared, for example, as follows:

B (Illa) 90 ml of pure concentrated hydrochloric acid were added to a mixture of 182 g lmole) of the sodium salt of oxalacetic acid dimethyl ester and 46 g 1 mole) of methylhydrazine in 500 ml of methanol, in the course of which the internal temperature rose to 40 50C After stirring for 3 hours, the volatile constituent was evaporated off and the residue was triturated with water, filtered off, dried and recrystallized from acetonitrile. 77g (50 percent of theory) of l-methyl-3- carbomethoxy-S-hydroxypyrazole of melting point 194 to l96C were obtained.

b) co-aa (IIIb) l6 g (0.1 mole) of l-methyi-3-carbomethoxy-5- hydroxypyrazole and 100 ml of approximately 26 percent strength ammonium hydroxide solution were stirred for 48 hours at room temperature. Thereafter the excess ammonia was stripped off under reduced pressure, the reaction mixture was diluted with water.

clarified and acidified with ml of pure concentrated hydrochloric acid and the precipitate formed was subsequently filtered off and dried on clay. 9 g (64 percent of theory) of l-methyl-3-carbamoyl-5-hydroxypyrazole of melting point 262C (with decomposition) were obtained.

c) C1 C1 CO-NH H (IIIc) Hydrogen chloride was slowly passed into a mixture of 34g (0.2 mole) of l-methyl-3-carboethoxy-5- hydroxypyrazole in 350 ml of isopropanol at 75 80C. After about 5 hours the mixture was concentrated under reduced pressure, the residue was dissolved in sodium hydroxide solution, the solution was filtered and treated with glacial acetic acid and the precipitate was filtered off, washed with water and dried on clay. g (54 percent of theory) of l-methyl-3- carboisopropoxy-S-hydroxypyrazole of melting point l53C were obtained.

The following compounds were prepared analogously:

Table 1 Structure Melting point '6 16 166C (IIIJ) 5 ooc n no- (Ina) 1470c Table l-Continucd Structure C OOC H I cn -cn -cn CH CQOC H HO- i I cn -cn -cn Melting point C (IIIf) '(IIIb) (IIIm) (IIIn) Table l-Continucd Table -(ontinued Structure Melting point: '0 m GO-Nl-l-Cl'i C1 01 0000 8 HO (1111p) 194 196C 1111 36% Cl CO-NH-CH If 3 EXAMPLE 2 HO- 0 (IIIq) 59 c 3 Cl CO--NH l CH3 (c it m t -o- (1 a CO NH N -CH T? CH3 ttoi (111:) 200 202 19 g (0.1 mole) of 0,0-diethylthionophosphoric acid diester chloride were added to a mixture of l7.6 g (0.1

mole) of l-methyl-3-carbamoyl-4-chloro-5-hydroxypyrazole and I5 g of potassium carbonate in 100 ml ol 3 5 acetonitrile and the mixture was subsequently warmed I to 80C for 8 hours, while stirring. The reaction mix- Pi ture was then cooled. poured into water and extracted (1115) 343 by shaking with benzene, the organic phase was washed 2 with water, the solvent was distilled off under reduced pressure and the residue was recrystallized from ethyl 004m acetate. 12 g (37 percent of theory) of 0,0-diethyl-0- 2 l-methyl-3-carbamoyl-4-chloro-pyrazolyl(5)1- llO- (Inn) 197 200C thionophosphoric acid ester of melting point 132C I were obtained. a r EXAMPLE 3 Cl CO-NH a) C1 CO C l-l tt o P-o- 2) (111v) 156C CHQ-CHQ'CN CH3 C1 2 33 g (0.2 mole) of triethylphosphite were added dropwtse, while stirring, to a solution 0f48 g (0.2 mole) H0- i 166C of l-methyl3-carboethoxy-4,4-dichloro-pyrazolonc(5) in 300 ml of benzene, in the course of which the tem- CH perature of the mixture rose to 30 40C. Thereafter 3 the reaction mixture was stirred for a further hour. the solvent was distilled off, the residue was dissolved in benzene, the organic phase was ashed with water and dried and the solvent was distilled off under reduced v 5 ressure, whereupon the residue solidified. 6| g (90 a 5 P I percent of theory) of 0,0-diethyl-0-l l-methyl-3- carboethoxy-4-chloropyrazol(5)yll-phosphoric acid 1 ester of melting point 34C were obtained. C1

5 EXAMPLE 4 (Vc) 136C -N 0 9 2 2 5 D 2 5 2 i'i:

l I C1 C1 COOC H CH CH -CN o l o as g (0.2 mole) of0,0-diethylphosphoric ucid dicstcr h-N B1 c chloride were added dropwise. while stirring. to a mixcH2 cH ture 0M2 g (0.2 mole) of l-cyanoethyl-3-eurboethoxy- S-hydroxypyrazole and 30 g of potassium carbonate in 300 ml of acetonitrile, in the course of which the temperature of the mixture rose to 35C. Thereafter the pressure and the residue was subjected to slight distil lation." 48 g (70 percent of theory) of 0.0-diethyl-O-l I cyanoethyl-B-carboethoxypyrazol( S )yl ]-phosphoric acid ester of refractive index n,, l.479l remained.

The following compounds were prepared unzilo gously to those of the preceding Examples:

Tablel Structure Physical properties (refractive index melting point C5 C COCXIH P A (c fl m -flln 1.48U

(4) I l CH COG'IH i 25 w fl m -eq m 1.4994 (5) e11 3 coocH (CH 0) ;-Q-@ melting point I (6) 4 50 52C CH 3 C1 COUCH (C H 0) ?-Q- l melting point H 48C ctr (7) melting point 3 6000285 22 (C H O) P-O- 1.4952

8 0000 11 (H w i -o 11 1.4996

45! gas 11 1 5552 P-O-fl 2) D 19 20 TABLE 2-Continucd structure Physical properties; (continued) (refractive index,

meltige point c) c1 cooc a n 1 melting point (CH Q) P-O- l (33) 103C 5 c1 cooc n 24 n CH CQOC g 2H5 melting point 3 35) 67% 9 c co-mi (C H 0) 1 melting point Q 01 co-nu o I ('57) melting point 0 H 0 1 c1 co-xm 1;, 2 (cn m r-o- I U melting point H 37 on co-rm s 2 n 20 n 1.5117 (c a m r o (.59) n cu -cn -cn 3 00-101 n melting point 0 o 2H5 )2? 0 Q1 1 114 116C s co-rm-cn I 2 5 2 megting point I (41) c coma-ca H (CH3O)2P-O- Y melting point 21 Q 22 TABLE 2-Continued 1 Structure Physical properties (continued) (refractive index,

me ltinp point c) c1 CO-NH-OH s s n I l (CrZ OMP-Orl (43) melting point 5 es e7o coma-CH f n meltin i t P 0 melting point (C2H50)2 (45) 70C eH -cH -CN s a 0) I I OZCZHS 2 5 213-0 (46) ff-1. 382

l CH2-('IH-CH3 0 2 5 5 (c a o) P-OU cm -c u-cn s 00 c n (611 50110 0G 2 2 5 cm -on-cn Plmclla test Solvent} parts by weight of acetone 60 E l l b t 23 pan y weight of amylml u After the specified periods of time, the degree of de- To produce a ham: preparation of a struction was determined as a percentage: X00 percent pound 1 pan by weight f he active compound was meant that all the caterpillars were killed whereas 0 mixed the (acd amount of solvent conaining the 65 Percent means hat none Of the caterpillars were stated amount of emulziifier and the concentrate was diluted with water to the desired concentration. The active compounds. the concentrations of the tie Cabbage leaves (Brassica olemcea) were sprayed tive compounds, the evaluation times and the results with the preparation of the active compound until dew can be seen from the following Table 3:

" moist and were then infested with caterpillars of the diamond-back moth (Plutella maculipennis).

23 24 2am 11mm Active compound Active D. of I compound 8 l com deltruotion tration in g :fter y weight (known) (B) Q-QQl 85 4.

EXAMPLE 6 Cabbage leaves (Brassica oleracea) were sprayed withthepreparationofthe active compound until dn'p- Phaedon larvae test ping wet and were then infested with mustard beetle Solvent: 3 parts by weight of acetone larvae (Phaedon cochleariae). Emulsifier: 1 part by weight of alkylaryl polyglycol After the specified periods of time, the degree of deether struction was determined in percent. Here, I00 percent To produce a suitable preparation of active commeans that all beetle larvae were killed. 0 percent pound, 1 part by weight of the active compound was means that none of the beetle larvae were killed. mixed with the stated amount of solvent containing the The active compounds, the concentrations of the acatated amount of emulsifier and the concentrate was tive compounds, the times of evaluation and the results diluted with water to the desired concentration. can be seen from the following Table 4:

(Phaedon larvae teat) Degree of 0989 Act: in compound Active compound concentration traction (known) (known) (C) Example 7 Cabbage plants (Brassica olemcea) which had been heavily infested with peach aphids (Myzus persi'cae) were sprayed with the preparation of the active com- Myzus test (contact action) Solvent: 3 parts by weight of acetone pound until dripping wet.

Emulsifier: 1 part by weight of alkylaryl polyglycol After the lpecified periods of time, the degree of deetruction was determined as a percentage: I00 percent other To produce a suitable preparation of active commeans that all the aphids were killed whereas 0 percent pound. l part by weight of the active compound was means that none of the aphids were killed. mixed with the stated amount of solvent containing the lite active compounds. the concentrations of the acstated amount of emulsifier and the concentrate was tive compounds, the evaluation times and the results diluted with water to the desired concentration. can be leen from the following Table 5:

Table 5 ()Lgzua teat) Active compound Active Degree of 1 compound destruction concenin p after 1 trat ion day in by 1 weight 3 3 .1 29 C H o 0 0 2 5 )2 o 0.001 0 (k wn) I 29 Table (continued) (gyms test) 7 Active" Degree of Tetranychus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alltylaryl polyglycol ether To produce a suitable preparation of active coinpound, 1 part by weight of the active compouhd was mixed with the stated amount of solvent containing the stated amount of emulsifier and the 'co'riceii trate' was diluted with water to the desired concentratioii.

Bean plants (Phaseolus vulgan's) which had a height These bean plants were heavily infested with all stages of development of the two-spotted spider mite (T8!- ranychus urn'cae).

After the specified periods of time, the effectiveness of approximately 10 30 cm were sprayed with the preparation of the active compound until dripping wet.

of the preparation of active compound was determined by counting the dead mites. The degree of destruction thus obtained was quoted in percent. 100 percent means that all the spider mites were killed and O per cent means that none of the spider mites were killed The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 6:

Table 6 (Tetran! chus test/resistant) Active compound Active Degree of compound destruction concen in 7 after tration 2 days in 7 by I weight w v, Z 3 0.1 (0 3 M -o- 0.01 0

n '32 EXAMPLE 9 f 7 I :1 vent had cemptett' evaporated. The amount of active L-rmm formptera 1 i a p 1 compound per squarecentimeter of filter paper varied j with the concentration of the solution of active compound used. AboutZS test insects were then placed in the Petri dilhand it' was covered with a glass lid.

' fl' t'e cohdition of the test insects was continuously observ edrflhetimewhich was necessary for a lOO percent a I p knock'dowh Q fect'tvasdetermined.

2.5 ml of the solution ot'active compound were pipet-' The test insects the active compounds, the concented into'a Petri dishQOnthe bottom of the Petri'dish' .9 trations of the active compounds and the periods of there was a'filter papcrwith a diameter of about 9.5 "time at which there is a I percent knock down effect cm. The. Petri dish remaineduncovered'utitilthe soli'can be seen from the following Table 7:

Test insects: Musca domestica Solvent: Acetone I Q I,

2 parts by weight of active compound were dissolved in l .000 parts by volume of solvent. The solution 'so'obtained was diluted with furthersolventto the-:desire lowerconcentrations.

ution in 7 w/v 0.2 6hrs .(C2H5O)2-O 0.02 8 hrs .(knotmHB) 3 0.2 80' 0.02 160' 0.002 6 hrs 2 0.2 0.02 I 1 0.002 8 hrs K20)" 0.2 70- 0.002 (2 hrs EXAMPLE ll LD test Test insects: Sitophilur granarius Solvent Acetone v 2 parts by weight of the active compound were taken up in L000 pans by volume of solvent. The solution so obtained was diluted with further solvent to the desired concentrations. it 2.5"ml of the solution of the active compound were It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit 5 and scope of the present invention.

What is claimed is:

1. An O-pyraaolotthiono)-phosphoric(phosphoniul acid ester of the formula RI I! pipetted into a Petri dish. on the bottom of the Petri x dish there was a filter paper with a diameter of about it, (1 9.5 cm. The Petri dish remained uncovered until the solvent had completely evaporated. The amount of ac- I tive compound per rn of filter paper varied with the 5 concentration of the solution of the active compound. About test insects were then-placed in the Petri dish i hi h and it w cp flc t a glass R is alkyl of one to six carbon atoms,

The condi i n of e test in was observed 3 y It is alkyl or alltoxy of one to six carbon atoms or after the commencement of the experiments. The de- 20 phenyl, struetion in percent was determined. R" is lower alkyl, cyano-lower alkyl or l,l-dioxythio- The active compounds, the concentrations of the aclane, tive compounds, the test insects and the results can be R' is carbo-lower alkoxy, carbamoyl, m0n0 lowcr seen from the following Table 9: alkylcarbamoyl or di-lower alkylcarbamoyl,

Table 9 (LD test)- Active compound Active Destruction compound in ,z;

concentrat ion of the solution in w/v CH i 3 0.2 100 (c a o) 0.02 o

I H (knoim) (c) 

1. AN O-PYRAZOLO(THIONO)-PHOSPHORIC(PHOSPHONIC) ACID ESTER OF THE FORMULA
 2. A compound according to claim 1 in which R is alkyl of one to four carbon atoms, R'' is alkyl or alkoxy of up to four carbon atoms or phenyl, R'''' is alkyl of one to four carbon atoms, cyanoethyl, 2-cyanopropyl or 1,1-dioxythiolane, R'''''' is carbomethoxy, carboethoxy, carboisopropoxy, carbamoyl or mono- or di-alkylcarbamoyl of up to three carbon atoms in each alkyl radical, and R'''''''' is hydrogen, chlorine, methyl or ethyl.
 3. A compound according to claim 1 wherein such compound is 0,0-dimethyl-0-(1-methyl-3-CARBOMETHOXYPYRAZOL(5)yl)-thionophosphoric acid ester of the formula
 4. A compound according to claim 1 wherein such compound is 0,0-dimethyl-0-(1-methyl-3-carboethoxy-4-chloropyrazol(5)yl) -thionophosphoric acid ester of the formula
 5. A compound according to claim 1 wherein such compound is 0,0-diethyl-0-(1-methyl-3-carboisopropoxypyrazol(5)yl)-thionophosphoric acid ester of the formula
 6. A compound according to claim 1 wherein such compound is 0,0-diethyl-0-(1-cyanoethyl-3-carboethoxy-4-chloropyrazol(5)yl) -thionophosphoric acid ester of the formula
 7. A compound according to claim 1 wherein such compound is 0,0-dimethyl-0-(1-methyl-3-N-methyl-carbamoyl-pyrazol(5)yl)-thionophosphoric acid ester of the formula 